We report an organo-molybdenumn oxide bronze that enables the fabrication of high-performance silver window electrodes for top-illuminated solution processed organic photovoltaics without complicating the process of device fabrication. This hybrid material combines the function of wide-band-gap interlayer for efficient hole extraction with the role of metal electrode seed layer, enabling the fabrication of highly transparent, low-sheet-resistance silver window electrodes. Additionally it is also processed from ethanol, which ensures orthogonality with a large range of solution processed organic semiconductors. The key organic component is the low cost small molecule 3-mercaptopropionic acid, which (i) promotes metal film formation and imparts robustness at low metal thickness, (ii) reduces the contact resistance at the Ag/molybdenumn oxide bronze interface, (iii) and greatly improves the film forming properties. Silver electrodes with a thickness of 8 nm deposited by simple vacuum evaporation onto this hybrid interlayer have a sheet resistance as low as 9.7 Ohms per square and mean transparency ∼80% over the wavelength range 400-900 nm without the aid of an antireflecting layer, which makes them well-matched to the needs of organic photovoltaics and applicable to perovskite photovoltaics. The application of this hybrid material is demonstrated in two types of top-illuminated organic photovoltaic devices.

The choice of metals suitable as the reflective substrate electrode for top-illuminated organic photovoltaics (OPVs) is extremely limited. Herein, we report a novel substrate electrode for this class of OPV architecture based on an Al | Cu | AlOx triple-layer structure, which offers a reflectivity comparable to that of Al over the wavelength range 400-900 nm, a work function suitable for efficient electron extraction in OPVs and high stability towards oxidation. In addition to demonstrating the advantage of this composite electrode over Al in model top-illuminated OPVs, we also present the results of a photoelectron spectroscopy study, which show that an oxidised 0.8 nm Al layer deposited by thermal evaporation onto an Al | Cu reflective substrate electrode is sufficient to block oxidation of the underlying Cu by air or during deposition of a ZnO1-x electron-transport layer. This is remarkable given that the self-limiting oxide thickness on Al metal is greater than 2 nm.

We show that for organic photovoltaics supported on a low workfunction reflective electron-extracting electrode, a hole-blocking layer is not required.